JPH02222449A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition of improved blend compatibility and shock resistance by using a resinous substance which is prepared by mixing a polyarylene sulfide and a phenoxy resin in an organic solvent at elevated temperature followed by precipitation and a thermoplastic resin. CONSTITUTION:The subject resin composition is composed of (A) 1 to 99 pts.wt. of a resinous substance (A1 content is 20 to 80wt.%) which is prepared by mixing A1: a polyarylene sulfide of the formula (Ar is arylene, preferably more than 70mole% is p-phenylene), A2: a phenoxy resin whose viscosity in 40 deg.C methyl ethyl ketone is 5X10<2>-10<5>cps, preferably 10<3>-5X10<4>cps and thermal decomposition point is about 420 deg.C, when needed, a modifier such as sulfur or organic peroxide in an organic solvent of 100 to 400 deg.C boiling point such as alpha- chloronaphthalene and effecting precipitation and (B) 99 to 1 pts.wt. of A1 and/or other thermoplastic resins.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a blend compatibility and impact resistance blend comprising a resinous material precipitated after mixing polyarylene sulfide and phenoxy resin in a high-temperature organic solvent. The present invention relates to a resin composition with improved properties.

Such compositions can be formed into various molded products by various molding methods such as injection molding, compression molding, extrusion molding, and pultrusion molding, and can be used in various fields.

(Prior Art and Problems to be Solved by the Invention) Polyarylene sulfide (hereinafter abbreviated as PAS) typified by polyphenylene sulfide (hereinafter abbreviated as PPS).

) itself has excellent heat resistance, solvent resistance, and flame retardancy, and is used in various molding fields including the electronics field.

However, while PAS has excellent performance, the unreinforced version is very brittle and has insufficient mechanical properties such as impact resistance, so its application as a molding material is limited. is the current situation.

Attempts have been made to improve properties such as impact resistance and flexibility by blending PAS with other thermoplastic resins, but the compatibility between the two is often insufficient, and simple Blends have not been successful. Therefore, for example, JP-A-59-58052, JP-A-59-155461
, No. 59-155462, and No. 59-164360, attempts have been made to blend PPS and other thermoplastic resins by using a novolak epoxy resin as a blend compatibilizer, but the PPS used has a low degree of crosslinking. In addition, the heat resistance of the epoxy resin during molding was poor, and it also had the disadvantage that it easily gelled, causing problems in workability during molding.

In addition, a block copolymer consisting of a PPS moiety and a polyphenylene sulfide sulfone moiety (JP-A-62-205
157) or a block copolymer consisting of a PPS moiety and a polysulfone moiety (JP-A-61-24775)
5), but it cannot be said to be easy because it involves producing a block copolymer, and the resin suitable for blending must also be selected from the same resin as the block part in the block copolymer. It had drawbacks such as a narrow range.

(Means for solving problems) The present inventors have developed a material with excellent heat resistance, chemical resistance, and rigidity.

As a result of intensive research to easily obtain a resin that can be blended with PAS and other thermoplastic resins in a wide range of ways, it is possible to improve properties such as impact resistance and flexibility while taking advantage of the properties of PAS. It has been discovered that a resinous material precipitated after mixing and phenoxy resin in a high-temperature organic solvent has excellent blend compatibility with PAS and other thermoplastic resins, and the present invention has been achieved.

That is, the present invention provides a resin composition consisting of a resinous material obtained by mixing polyarylene sulfide and phenoxy resin in a high-temperature organic solvent and precipitating the mixture, and polyarylene sulfide and/or other thermoplastic resin. It is.

PAS, which is a component of the resinous substance in the present invention and can be mixed with the resinous substance, has the structural formula (-Ar-S
-), (Ar: arylene group). Here, -Ar- of the arylene group is a divalent aromatic residue containing a 6-carbon aromatic ring such as p-phenylene, m-phenylene, 0-phenylene, 2,6 naphthalene, 4.4" biphenylene, Furthermore, each aromatic ring contains F, C1l, Br,, CH.

Substituents such as these may also be introduced. These may be homopolymers, random copolymers, or block copolymers.

Particularly, PAS preferred for use in the present invention is 300 °C 110
The real part [η'] of the complex viscosity at 0 rad/see is 1
0”~105poise, preferably 500~500
It has a melt viscosity within the range of 0 poise and the above P
70 mol% or more of the -Ar portion in the general structural formula of AS,
Particularly preferred is 90 mol% or more of PPS. The shape of the molecular chain of PPS used is linear, branched, partially crosslinked, or a mixture thereof. In addition, PPS included in PPS or formed by the synthesis process or post-processing process
Commercially available products include Frilaps Vetroleum's Rydon PPS and Higashishino Higashi PPS.

On the other hand, the phenoxy resin, which is a constituent component of the resinous material of the present invention together with the PAS, is a thermoplastic polyether resin that does not have epoxy groups at both ends and is synthesized using bisphenol A and epichlorohydrin as main raw materials.

Preferred phenoxy resins for use in the present invention have a solution viscosity of 40% non-volatile content in methyl ethyl ketone (MEK) solution in the range of 5 x 102 to 10' cps, preferably 103 to 5 x 10' cps.

Such phenoxy resin has a thermal decomposition temperature of about 420° according to thermogravimetric analysis (TGA measurement, 10 weight loss in air).
C (UCAR phenoxy resin PKHH grade) and PA
It is higher than the upper limit of the normal molding temperature of S, 400°C, and has excellent heat resistance.

Commercially available phenoxy resins include Union Carbide's tlcAR phenoxy resin (PKH) [, PKHJ
SPKHM 30, etc.).

The resinous substance used in the composition of the present invention is the above-mentioned P
AS and phenoxy resin are heated at high temperatures, sometimes at high temperatures.
It is obtained by mixing in an organic solvent under pressure and then precipitating it.

When PAS and phenoxy resin are mixed in a high-temperature organic solvent, modifiers such as sulfur and organic peroxides can be added as necessary to enhance the effectiveness of the resulting resinous material. be.

The proportion of PAS in resinous substances is 20-80%
and preferably 30 to 70% by weight.

The organic solvent used for mixing is a solvent that substantially dissolves or swells the PAS and phenoxy resin, such as α-chloronaphthalene, α-methylnaphthalene, n-) H) Lt-2
- Pyrrolidone, diphenyl ether, diphenyl, etc. are used. These may be used alone or in combination of two or more.

The mixing temperature cannot be unconditionally defined as it varies depending on the type of solvent used, the type of PAS and phenoxy resin, and the mixing ratio of these, but it is usually 100-400 ml.
00°C. Below 100°C, resinous substances that improve blend compatibility cannot be obtained;
If it exceeds this, the decomposition of PAS and phenoxy resin will be significant, which is not preferable.

There is no limit to the amount of organic solvent used as long as the resin can be substantially dissolved and mixed, but in order to increase productivity, it is desirable to increase the concentration as much as possible.

The resin-like substance can be precipitated by one or a combination of various methods for separating a polymeric substance from a polymeric solution, such as a cooling precipitation method, a precipitation method by adding a non-solvent, and a solvent distillation method.

The resin composition of the present invention is made by blending PAS and/or other thermoplastic resins with such resinous substances.

As the other thermoplastic resin used in this case, any of the various thermoplastic resins described in known literature regarding PAS can be used, such as polysulfone, polyethersulfone, polyarylsulfone, polyetherketone, and polysulfone. Ether ether ketone, polyarylate, phenylene oxide, thermoplastic polyester, polyamide, polycarbonate, polyacecool, polyamideimide, polyetherimide, polyimide, fluororesin, ethylene, propylene, butylene, pentene, butadiene, isoprene, styrene, (meth) Acrylic acid ester,
Homopolymers or copolymers of monomers such as (meth)acrylonitrile, block and graft copolymers, and polyolefins modified with maleic acid grafted ethylene-butene copolymers, sulfuric acid, oxidizing agents, etc. Examples include modified (co)polymers such as: Among these, preferred are polysulfone, polyethersulfone, and polyaryl sulfone having a repeating unit; polyetherketone and polyetheretherketone having a repeating unit; bisphenol derivatives such as bisphenol A, isophthalic acid, terephthalic acid, or derivatives thereof. Polyarylates suitably synthesized from dibasic acids such as; polymers of 2,6-disubstituted phenols or 2,6-disubstituted phenols;
Polyphenylene oxide, which is a polymer of substituted phenol and polyhydric phenol; polyethylene terephthalate;
Thermoplastic polyesters represented by polybutylene terephthalate and poly(cyclohexane dimethylene terephthalate); nylon-6, nylon-66, nylon-6
4. Polyamide represented by nylon-MXD 6 (copolymer of m-xylene diamine and adipic acid); phenoxy resin, a thermoplastic polyether whose main raw materials are bisphenol A and epichlorohydrin; based on bisphenols, A polycarbon obtained by reacting this with diphenyl carbonate or phosgene (wherein, Ar is a trivalent aromatic group, and R is a divalent aromatic group).

and/or a divalent aliphatic group (R' is hydrogen, an aliphatic group, or a phenyl group), and the like. (Unexamined Japanese Patent Publication No. 59-64667, No. 59-155461
, No. 59-155462, No. 59-164360) In the resin composition of the present invention, when PAS is used in combination with 1 to 99 parts by weight, preferably 5 to 60 parts by weight, of the resinous substance described above, 99 to 1 part by weight of PAS, preferably 95
-60 parts by weight, and when used in combination with other thermoplastic resins, it contains 99 to 1 parts by weight, preferably 5 to 60 parts by weight. (However, the total shall be 100 parts by weight.) When PAS and other thermoplastic resins are used together in the resinous substance, (resinous substance) / (PPS)
/(other thermoplastic resin)=1~60/99~20/1~
80, preferably 2 to 40/95 to 3015 to 70 (total 100 parts by weight).

It is possible to blend a fibrous or granular reinforcing agent into the composition of the present invention as needed, and by blending it in a range of usually 5 to 300% by weight based on the resin composition, strength and rigidity can be improved. , heat resistance and dimensional stability can be improved. Examples of fibrous reinforcing agents include carbon fiber, glass fiber,
Silane glass fiber, ceramic fiber, asbestos fiber,
Examples include metal fibers. Further, examples of the granular reinforcing agent include silicates such as mica and talc, carbonates, sulfates, metal oxides, glass beads, and silica.

Two or more of these may be used in combination, and if necessary, they may be treated with a coupling agent such as a silane type.

The method for preparing the resin composition of the present invention is not particularly limited, and may be, for example, a method of melt-kneading with a conventional melt extruder and pelletizing. The melting temperature is preferably 280 to 400°C, and temperatures exceeding 400°C are not preferred because the resin will decompose.

(Effects of the Invention) The resin composition of the present invention can be used, for example, in electrical/electronic parts such as connectors, printed circuit boards, and molded products for sealing, in automobile parts such as lamp reflector 1 and various electrical components, in various buildings, automobiles, etc. Injection molding and compression molding of interior materials for aircraft, leisure and sports equipment such as tennis rackets, golf clubs, fishing rods, precision parts such as OA equipment parts and camera parts, composite sheets, pipes, etc.
It is used as a molding material with excellent impact resistance in various molding fields such as extrusion molding and pultrusion molding of sheets, and fibers.

(Example) The invention will be explained by way of example.

Example 1, Comparative Example 1 PP5 (Rydon PRO-6, Philips Vetroleum Co., Ltd. (y+
"3 = 800~1000poise) and 7'
Z phenoxy resin (UCAR phenoxy-PKHH, manufactured by Union Carbide, 4500 to 7000 cps (4
)) in 0% MEK, blending ratio 50150, total resin concentration 1
The solution was blended with stirring for about 1 hour, and the mixture was cooled and precipitated while stirring. Ethanol was further added to separate the precipitate, and the precipitate was vacuum-dried at 120° C. for about 5 hours.

Mixing ratio of PPS, nylon-66 (manufactured by BASF) and resinous substance as shown in Table 1 (the amount of resinous substance added is PP
A blend of 5% by weight of the total amount of S and nylon-66 was melt-kneaded in an extruder at 290 to 310°C, and then formed into a pellet. A rod-shaped sample piece with a cross-sectional area of 3.15 x 3.15 mm was prepared using an injection molding machine, and heat treated at a temperature of 140°C for about 1 hour.Then, it was subjected to an Izot impact test at a room temperature of 23°C. (without notches) to examine impact resistance.

In either case, injection molding could be carried out smoothly without gelation.

As Comparative Example 1, a case in which no resinous substance was included was investigated. The results are summarized in Table 1.

It can be seen that the Izod impact value is improved by adding a resinous substance.

Examples 2 to 8, Comparative Examples 2 to 8 Using the resinous material (PPS/phenoxy resin = 50150) prepared in Example 1, this was
system (Example 2), PPS/polyethersulfone system (Example 3), PPS/polysulfone system (Example 4), PP
S/polybutylene terephthalate system (Example 5) and P
It was added to each of the PS/polycarbonate-based (Example 6), PPS/modified polyphenylene oxide-based (Example 7), and PPS/polyarylate-based (Example day) compositions in the same manner as in Example 1, and subjected to an Izot impact test. (without notches) to examine impact resistance. In either case, the melt viscosity was suitable and injection molding could be performed smoothly without gelation.

For comparison, a case in which no resinous substance was added was also investigated. The results are shown in Tables 2 to 8.

The resin used was PPS (Rydon PRO-6),
Nylon-6 (manufactured by Kanebo), Nylon-66 (BA
manufactured by SF), polyether sulfone (pH! 53600)
, manufactured by IC1), polysulfone (UDEL P-350
0, manufactured by Union Carbide), polybutylene terephthalate (Planac BT-120, manufactured by Dainippon Ink and Chemicals), polycarbonate (Niepilon S-2000)
, manufactured by Mitsubishi Gas Chemical Co., Ltd.), modified polyphenylene oxide (Iupiace AV60, manufactured by Mitsubishi Gas Chemical Company), and polyether) (U Polyether-100, manufactured by Unitika Co., Ltd.).

Example 9, PPS (Rydon PRO-6) and the resinous material prepared in Example 1 (PRO-6/UCAR-PKHH=
Using a resin composition having a compounding ratio of 50150) as shown in Table 9, an Izot impact test (without notches) and a tensile impact test were conducted to examine impact resistance. In addition, in the case of Izotsu impact, a rod-shaped object with a cross-sectional area of 3.15 x 3.15 cylinder 2 is used, and in the case of tensile impact, a rod-shaped object with a diameter of 1.5 mmφ and a length of 8 is used.
A bell-shaped one with a size of 0 was used. The results are shown in Table 9.

Example 10 In place of the phenoxy resin (UCAR phenoxy-PKIIFI) used in Example 9, IICAR phenoxy-
PKHM 30 J (manufactured by Uni, T-Carbide Co., Ltd.,
The impact resistance was examined in the same manner as in Example 9 except that the impact resistance was 1500 to 2000 cps (40% MEK). The results are shown in Table 10.

/ / Comparative Examples 9 to 11 Nylon-66 (used in the above examples) was used as a thermoplastic resin to be blended with PPS (Rydon PRO-6).
Comparative Example 9), polycarbonate (Comparative Example 10), polybutylene terephthalate (Comparative Example 11), and further PP
A sample for an impact test was prepared using a resin composition using a novolak epoxy resin (Epicron N695, manufactured by Dainippon Ink Chemical Industries, Ltd.) as a blend compatibilizer for S and the thermoplastic resin.

The blending weight ratio of PPS/each thermoplastic resin/novolak epoxy resin is (50/48/2) and (80/18/2)
In each case, gelation occurred during molding and the melt viscosity increased, making it impossible to create sample pieces.

Comparative Examples 12 to 14 Using polyether sulfone (Comparative Example 12), polyarylate (Comparative Example 13), and modified polyphenylene oxide (Comparative Example 14), the melting temperature was 3.
Injection molding was attempted at 30-350"C, but the melt viscosity was so high that smooth injection could not be performed.

Example 11.12/Comparative Example 15.16 Using the resinous material (PPS/phenoxy resin = 50150) prepared in Example 1, it was mixed with PPS/ABS resin system (Example 11), PPS/polyethylene system (Example 11), and PPS/polyethylene system (Example 11). Example 12
) was added to each composition in the same manner as in Example 1, and an Izot impact test (without notches) was conducted to examine impact resistance. In either case, the melt viscosity was suitable and injection molding could be carried out smoothly without gelling.

As a comparative example, a case in which no resinous substance was added was also investigated. The results are shown in Table 11.12.

The resin used was pps (Rydon PRO-6),
They are ABS resin (Stylac, manufactured by Asahi Kasei Kogyo Co., Ltd.) and polyethylene (Shorex F 5010, manufactured by Showa Denko Co., Ltd.).

Claims (1)

[Claims] 1. A resin composition consisting of a resinous substance obtained by mixing polyarylene sulfide and a phenoxy resin in a high-temperature organic solvent and precipitating the mixture, and polyarylene sulfide and/or another thermoplastic resin.